Phenylazo-2,3-hydroxynaphthoic acid amides containing diphenylureas



United States Patent "i 3,472,834

Patented Oct. 14, 19 69 Of special interest are dyestufis of the formula 3,472,834 t (2) X PHENYLAZO-2,3-HYDROXYNAPHTHOIC ACID AMIDES CONTAINING DIPHENYLUREAS Karl Ronco, Riehen, and Armand Roueche, 'Neu- N- Allschwil, Switzerland, assignors to Ciba Limited, 5 ii Basel, Switzerland, :1 company of Switzerland v I No Drawing. Filed Mar. 28, 1966, Ser. No. 537,720 0H Y Z Claims priority, application Switzerlan ;16,/6A6pr. 2, 1965, i 1

' 4,588/65; Mar. 9, 1966, 3,3

Int. 'Cl. C07c 107/08 7 10 X CONH- US. Cl. 260-203 7 Claims Y w v v 2 in which represents a hydrogen or halogen atom or an n 1 ABSTRACT OF THE D SC R alkoxy group, X represents a hydrogen or halogen atom, Compounds of the formula 4 a X and X represent hydrogen or halogen atoms or alkyl, alkoxy, phenoxy, nitro, cyano, carbalkoxy, aliphatic acyl- 1 a amino, carbamido or trifluoromethyl groups, Y and Y OR represent hydrogen or halogen atoms or alkyl, trifiuoromethyl or alkoxy groups, Z represents a hydrogen or \CONH- RS I\IRCOI\IH R4 halogen atom and Z and Z represent hydrogen or halogen atoms or alkyl, alkoxy, nitro, cyano, carbalkoxy, aliin which R represents a benzene residue that may be Phatic acylamino trifluol'om'ithyl g p and dyestuffs substituted, R represents a naphthalene residue in which of the formula the azo, hydroxy and carboxylic acid amide groups are v in 1,2,3-position, R represents a phenylene residueand R represents an aryl, alkyl or aralkyl residue, are valu- N w Z4 able monoazo pigments of superior migration fastness, Z! useful in spin-dyeing of fibers and in the coloration of JONH plastic masses.

' OH Y Z Z: The present invention provides valuable new monoazo CONH pigments of the formula z, (1) N=N-R1 OH in which V represents a halogen atom or an alkyl, alkoxy or carbalkoxy group, W and Z represent hydrogen or halogen atoms, Z and Z represent hydrogen or halogen CONH-R -NHCONH-Rf atoms or alkyl, alkoxy, nitro, cyano, carbalkoxy or tri- 4O fluoromethyl groups and Y Y Z Z and Z have the in which R represents a benzene residue that may be meanings given b substituted, R represents a naphthalene residue in which Because the products of the invention are pigments the 310, Y Y and ql acid amide groups are they must not contain groups imparting solubility in waill 'P 3 l'ePresents a Phenylene residue and ter in particular acidic groups imparting solubility in wa- 4 represents an aryl, alkyl afalkyl l'esidmh More P ter, for example, sulphonic acid groups or carboxylic acid cifically, these compounds are those of the formu a gronps e The new product may be obtained when (a) a car- Xfl boxylic acid halide of the formula i 4) N=NR1 111 KB l/OH on Y R2 (Jo-Hal X OONH- in which R and R have the meanings given above, is

' NHCONHR condensed with a monamine of the formula in which R and R have the meanings given above, or (b) a diazotized aminobenzene is coupled with a naphthol of the formula in which R is a member selected from the group consisting of lower alkyl, benzyl, phenyl and naphthyl and phenyl and naphthyl substituted by chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy, trifluoromethyl or lower alkanoylamino groups, X is a member (5) OH selected from the group consisting of hydrogen, chlorine Ra and bromine atoms and lower alkoxy groups, X is a mem- I \CONEFRFNHQONH R4 ber selected from the group consisting of hydrogen, chlotime and bromine atoms, X and X each represent hydroor (c) a diazotized aminobenzene is coupled with a gen, chlorine and bromine atoms, lower alkyl, lower alknaphthol of the formula oxy, phenoxy, nitro, cyano, lower carbalkoxy, carbophenyl- CHM amido, lower alkanoylamino or trifluoromethyl groups, Y 0H and Y each represent members selected from the group consisting of hydrogen, chlorine and bromine atoms, lower alkyl, trifluoromethyl, and lower alkoxy groups. CONH"'R3 VNHCONH R in which Formulae A represents the residue of an amine and R R and R have the meanings given above.

Specially valuable pigments may be obtained when a carboxylic acid chloride of the formula i -CT? bl X (loci in which X represents a hydrogen or halogen atom or an alkoxy group, X represents a hydrogen or halogen atom, and X and X represent hydrogen or halogen atoms or alkyl, alkoxy, phenoxy, nitro, cyano, carbalkoxy, carbarnido, aliphatic acylamino or trifluoromethyl groups, is condensed with an amine of the formula Z: Q-NHC ONE- HgN in which Y and Y each represents a hydrogen or halogen atom or an alkyl or alkoxy group, Z represents a hydrogen or halogen atom and Z and Z each represent hydrogen or halogen atoms or alkyl, alkoxy, nitro, cyano, carbalkoxy, aliphatic acylamino or trifiuoromethyl groups.

The carboxylic acids on which the halides are based may be obtained by coupling a diazo compound of an aminobenzene, especially one of the formula with a 2,3-hydroxynaphthoic acid, especially one of the formula X- COOH in which X represents a hydrogen or halogen atom or an alkoxy group.

As examples of aminobenzenes of the Formula 9 the following may be mentioned: aniline, and especially halogenated anilines, for example, 2-, 3- and 4-chloraniline, 3,4-dichloraniline, 2,3-dichloraniline, 2,4-dichloraniline, 2,5-dichloraniline, 2,6-dichloraniline, 2,4,5-trichloraniline, 2,4,6-trichloraniline, 2-, 3-, or 4-bromaniline, 2,4-dibromaniline, 2,5-dibromaniline, 2-methyl-5- chloraniline, Z-methyl 4-chloraniline, 2-methyl-3-chloraniline, 2 chloro trifiuoromethylaniline, nitranilines, for example, 2-, 3- and 4-nitraniline, 4-chloro-2-nitraniline, 2-chloro-4-nitraniline, 4-methyl-3-nitraniline, 2,4-dimethyl 3 nitraniline, Z-methyI-S-nitraniline, 2-methyl-4- nitraniline, alkoxyanilines and phenoxyanilines, for example, 2- and 4-methoxyaniline, 2- and 4-ethoxyaniline, 3-chloro-4-methoxyaniline, 2-methoxy S-nitraniline, 2- methoxy S-chloraniline, 2-methoxy S-trifiuoromethylaniline, 2-amino 4 trifluoromethyl 4'-chlorodiphenylether, 2-nitro-4-ethoxyaniline, 2-methoxy 4-chloro-5- methylaniline, 2-amino 4-chlorodiphenylether, 3-arnin0- 2,4-dichlorodiphenylether, 2-amino 4,4 dichlorodiphenylether, l-amino-Z-carboxylic acid methylester, 1- amino-2-chloro-5-carboxylic acid methylester, Z-amino- 5 nitrobenzoic acid methylester, l-amino-Z-methylbenzene-S-carboxylic acid methylester, 1-amino-2-chlorobenzene-S-carboxylic acid methylamide, 2-amino-4-trifluoromethyldiphenylether.

As examples of aminobenzenes of the Formula 10 the following may be mentioned:

4-methyl-3 -aminobenzoic acid-2'-chloro-5'-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2,5'-dichloroanilide,

4-chloro-3 -aminobenzoic acid-2'-chloro-5'-carbomethoxyanilide,

4-chloro-3-aminobenzoic acid-3-chloranilide,

4-chloro-3-aminobenzoic acid-2'-chloro-5-trifluoromethylanilide,

4-chloro-3-aminobenzoic acid-3-trifiuoromethylanilide,

4-chloro-3-aminobenzoic acid-3',5'-bistrifluoromethylanilide,

4-chloro-3-aminobenzoic acid-2',4,5-trichloranilide,

2,4-dichloro-5-aminobenzoic acid-2,5'-dichloranilide,

2,4-dichloro-5-aminobenzoic acid-2',4'-dichloranilide,

2,4-dichloro-5-aminobenzoic acid-3'-trifluoromethylanilide,

2,4-dichloro-S-aminobenzoic acid-3-chloranilide,

5-amino-4-methoxy-2-chlorobenzoic acid-3 '-trifluoromethylanilide,

4-methyl-3-aminobenzoic acid-2',5'-dichloranilide,

.4-methyl-3-aminobenzoic acid-3-trifiuoromethylanilide,

4-methoxy-3-aminobenzoic acid-3'-chloranilide,

4-methoxy-3-aminobenzoic acid-2',5'-dichloranilide,

4-methoxy-3-aminobenzoic acid-2,4,5-trichloranilide,

4-carbomethoxy-3-aminobenzoic acid anilide,

4-methoxy-3-aminobenzoic acid-3'-trifiuoromethylanilide,

4-carbethoxy-3-aminobenzoic acid-2',5'-dichloranilide,

4-methoxy-3-aminobenzoic acid-3',5-bis-trifluoromethylanilide,

4-methoxy-3-aminobenzoic acid-2'-chloro-S'-trifluoromethylanilide,

4-methoxy-3-aminobenzoic acid-2',5'-dirnethoxy-4- chloranilide,

4-methoxy-3 -aminobenzoic acid-2',5'-dimethyl-4'-chloranilide.

The azo dyestuff carboxylic acids obtained may be treated with agents capable of converting carboxylic acids into their halides, for example, their chlorides or bromides, such agents being, in particular, phosphorus halides, for example, phosphorus pentabromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxyhalides and preferably thionyl chloride.

The treatment with such acid halogenating agents is advantageously carried out in an inert organic solvent, for example, dimethylformamide, a chlorobenzene, for example, monochlorobenzene or dichlorobenzene, toluene, xylene or nitrobenzene; the last five solvents may be used together with dimethylformamide.

When preparing the carboxylic acid halides it is generally advantageous first to dry the azo compounds which have been prepared in aqueous medium, or to free them from water by azeotropic distillation in an organic solvent; if desired, azeotropic drying may be carried out immediately prior to the treatment with the acid halogenating agents.

The azo dyestutf carboxylic acid chlorides obtained are advantageously condensed with monamines of the Formula 8. The following amines are examples:

4-aminodiphenylurea, 4-amino-4'-chlorodiphenylurea, 4-amino-4'-methyl-diphenylurea, 4-amino-4-methoxdiphenylurea, 4-amino2-methyldiphenylurea, 4-amino-3 -methyldiphenylurea, 4-amino-Z-chlorodiphenylurea,

4-amino-2,S-dimethyldiphenylurea, 4-amino-2,5-dimethyl-4'-chlorodiphenylurea, 4-amino-2,5,4-trimethyldiphenylurea, 4-amino-2,S-dichlorodiphenylurea, {t-amino-Z,S,4-trichlorodiphenylurea, 4-amino-2-methyl-5-chlorodiphenylurea, 4-amino-2-methoxy-5-chlorodiphenylurea, 4amino-2-methoxy-5,4-dichlorodiphenylurea, 4-amino-2,S-dichloro-4'-methoxydiphenylurea, 4-amino-2,4-dichlorodiphenylurea, 4-amino-2-chloro-3'-trifluoromethyldiphenylurea, 4-amino-2,5-dimethyl-2-methoxy-4'-chlorodiphenylurea, 4-amino-2,5-(dimethylphenyl)-a-naphthylurea, 4-amino2,5- (dichlorophenyl) -fi-naphthylurea, 4-aminophenyl-wnaphthylurea, 4-amino-2-methylphenyl-a-naphthylurea, 4-amino-2,5-dimethyl-3-chlorodiphenylurea, 4-amino-2,5-dimethyl-4'-methoxydiphenylurea, 4- amino-2,5-dirnethyl-4'-methyldiphenylurea, 4-amino-2,5-dichloro-3'-chlorodiphenylurea, 4-amino-2,5-dichloro-4'-methyldiphenylurea, 4-,amino- 5-methoxy-2-chlorodiphenylurea, 3-amino-4,2'-dichloro-5'-trifluoromethyldiphenylurea, 3-amino-4,2- dichlor0-5-carbomethoxydiphenylurea, 3-amino-4,2',5'-trichlorodiphenylurea, 4-amino-3'-trifluoromethyldiphenylurea, 4-amino-2-chloro-5'trifluoromethyldiphenylurea, 4-amino-2'-chloro-5'-carbomethoxydiphenylurea, 4-amino-2',5-dichlorodiphenylurea, 4-amino4-methoxydiphenylurea, 4-amino-4'-acetylaminodiphenylurea, 4-amino-4'-carbomethoxydiphenylurea, 4-amino-2',4'-dichlorodiphenylurea, 4-amino-2,S-dimethoxydiphenylurea, 4-amino-2,5-dimethoxy-4'-chlorodiphenylurea, I 4-a1nino-2,5-dimethylphenyl-benzylurea, 4-aminophenylbenzylurea,

4-aminophenylbutylurea, 4-aminophenylmethylurea, 4-amino-5-chloro-2-methoxy-4-acetylaminodiphenylurea, 4-amino-2,5-dimethyl-4'-acetylaminodiphenylurea, 4-amino-5-chloro-2-meth-oxyphenylmethylurea, 4-amino-2,5-dimethylphenylmethylurea, 4-amino-2,5-dichlorophenylmethylurea, 4-amino-2',4',5'-trichloro-2-methoxydiphenylurea and 4amino-2-methylphenylmethylurea.

The condensation of the carboxylic acid halides of the kinds defined above with the amines is advantageously carried out in an anhydrous medium. Under these conditions, condensation proceeds surpringly easily, even at temperatures within the boiling range of the common organic solvents, for example, toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. It is generally advantageous to use an agent capable of binding acid, for example, anhydrous sodium acetate or pyridine, in order to accelerate the reaction. Some of the pigments obtained are crystalline and some are amorphous. They are generally obtained in very good yield and in a pure state. It is advantageous first of all to isolate the acid chlorides obtained from the carboxylic acids. In some cases, however, isolation of the acid chlorides can be dispensed with without harm, and condensation carried out immediately after the preparation of the carboxylic acid chlorides.

In method (b) of the process of the invention the new products may be obtained when a diazotized aminobenzene, especially one of the Formula 9 or 10, is coupled with a naphthol of the Formula 5, especially one of the formula ()H Y Z1 2 X C ONH -NHC ONH- 2g in' which X, Y Y Z Z and Z have the meanings given about.

Coupling is effected by the gradual addition of the aqueous alkaline solution of the coupling component to the acid solution of the diazonium salt. The alkali hydroxide required to dissolve the coupling component is advantageously used in an amount sufiicient to neutralize the mineral acid liberated from the diazonium salt during coupling. Coupling is advantageously carried out at a pH value of 4 to 6. The pH is advantageously adjusted by the addition of a buffer. Suitable bufIers are, for example, the salts especially the alkali metal salts, of formic acid, phosphoric acid or especially acetic acid. The alkaline solution of the coupling component advantageously contains a wetting, dispersing or emulsifying agent, for example, an aralkylsulphonate, for example, dodecylbenzene sulphonate or the sodium salt of l,l-naphthylmethane sulphonic acid, polycondensation products of alkylene oxides, for example, the product obtained by reacting ethylene oxide with para-tertiary-octylphenol, and also alkyl esters of sulphoricinoleates, for example, n-butylsulphoricinoleate. The dispersion of the coupling component may also advantageously contain a protective colloid, for example, methylcellulose or small amounts of inert organic solvents that are sparingly soluble or insoluble in water, for example, aromatic hydrocarbons that may be halogenated or nitrated, for example, benzene, toluene, xylene, chlorobenzene, dichlorobenzenes or nitrobenzene, as well as aliphatic halogenated hydrocarbons, for example, carbon tetrachloride or trichloroethylene, and organic solvents miscible with water, for example, acetone, methylethylketone, methanol, ethanol and isopropanol.

Coupling may also advantageously be carried out in a manner such that an acidic solution of the diazonium salt is continuously combined with an alkaline solution of the coupling component in a mixing nozzle, in which process coupling takes place instantaneously. Care must be taken to ensure that diazo solution and coupling component are present in the mixing nozzle in equimolecular proportions, it being advantageous to provide for a small excess of coupling component. The simplest method of doing this is to control the pH of the liquid in the mixing nozzle. It is also important to ensure that both solutions are in a state of turbulence in the mixing nozzle. The pigment dispersion so formed is continuously drawn off from the mixing nozzle and the pigment is isolated by filtration.

In method c of the process of the invention, the new pigments may be obtained by coupling a diazotized aminobenzene, especially one of the Formula 9, with a naphthol of the Formula '6, in which A preferably represents the residue of an amine of the formula in which R represents a hydrogen atom or an alkyl residue and R represents an alkyl residue, and in which the residues R and R together with the nitrogen atom, may form a heterocyclic ring. As examples there may be mentioned the residues of methylamine, dimethylamine, diethylamine, diethanolamine, pyrrolidine, piperidine and morpholine. The compounds of the Formula 6 are obtainable by reacting the compounds of the Formula 5 with formaldehyde and a primary or secondary amine.

The residue -CH A is split ofr during the coupling process and replaced by the azo group. Coupling is advantageously carried out in an acid medium.

The new products are valuable pigments and can be used for a very wide variety of purposes. For example, they may be used in a state of fine division for the spindyeing of filament and staple-fibre viscose rayon, cellulose ethers and esters, polyamides, polyurethanes, and polyesters, as well as in the preparation of coloured lacquers and as lake formers. They may also be used for colouring solutions and products made from cellulose acetate, nitrocellulose, natural resins and synthetic resins, for example polymerisation or condensation resins, for example, aminoplasts, alkyd resins, phenoplasts, polyoleyl-4-amino)-phenyl-N-phenylurea and 800 parts of orthodichlorobenzene. Subsequently, the sparingly soluble pig ment, which is-in the form of fine crystals, is isolated by filtration while hot, washed with hot ortho-dichlorobenzene, alcohol and hot water, and then dried in vacuo at fines, for example, polystyrene, polyvinyl chloride, poly- 5 70 to 80 C. The product so obtained of the formula ethylene, polypropylene, polyacrylonitrle, rubber, casein, C1 silicones and silicone resins. They can also be used with advantage in the preparation of coloured pencils, cos- O metic preparations and laminated sheet material. ILL

Compared with the products described in French patent specification No. 784,220, which contain a benzoylamino group instead of the ureido group, the pigments obtainable by the process of the present invention are dis- I tinguished by a better fastness to migration. CONH NHC Q The following examples illustrate the invention. Unless otherwise stated, the parts and percentages are by H3O weight.

EXAMPLE 1 1s a red pigment WhlCh 1s sparingly soluble to Insoluble in the common solvents and which colours polyvinyl chlo- 84 parts of the dyestufi obtained by diazotising 5 triride film and lacquers scarlet red tints possessing an exfiuoromethyl-Z-chloro-l-aminobenzene in aqueous hydrocellent fastness to light, migration and overstripe bleedchloric acid with sodium nitrite and coupling with 2,3- ing. hydroxynaphthoic acid are heated with 1,500 parts of ben- The azo dyestulf monocarboxylic acids, obtainable zene, parts of thionyl chloride and 2 parts of dimethyl- 25 from the mononuclear diazo components listed in column formamide for one hour at to C. while stirring. I of the following table and the coupling components After cooling the reaction mixture, the uniformly crystallisted in column II, can be reacted via the monoazo dyeline mono-carboxylic acid chloride of the dyestufi is isostufi monocarboxylic acid chlorides with 1 mol of the lated by filtration, washed with cold benzene and then aromatic monamines containing urea groups listed in coldried in vacuo at 50 to 60 C. 0 umn III in the manner described in the first and second 8.3 parts of the chloride so obtained are heated for 12 paragraphs of this example. Column IV indicates the tints hours at to C. with 5.5 parts of N-(2,5-dimethobtainable with the pigments in polyvinyl chloride film.

I II III IV 2-Inethoxy-5-trifiuoromethylaniline.. 2,3-hydroxynaphtho1c acid 4-amino-2,5-dimethyldiphenylurea Red.

2-cl1loro 5-trifluoromethylaniline do 4-amino-2,5-dimethyl-3chlorodiphenylurea 4-amino-2-methyl-4-chlorodiphenylurea 4-amiuo-2,5,4'-trirnethyldiphenylurea 4arnino-2,5dimethyl-4-chlorodiphenylurea 4-amino-2-methyldiphenylurea 4-amino-2,5,4-trieh1or0diphenylurea 4-amino-2,5-dich1oro-4-methoxydiphenylurea do 4-amino-2,5,3-trichlorodiphenylurea-... Red. ..do 4-a1nirio-2,5-dichlorodiphenylurea- Red. -.do. 4-ann'no-4-chlorodiphenylurea Red. .-do 4-aminodiphenylurea... Red. do tamino-f-methoxydiphenylurea Red. do 4-amino-2-methoxy-5chlorodiphenylurea Red.

do.. 4-amino-2-n1ethoxy-5,4-dichlorodiphenylurea. Orange do- 4-amino-2,5,4-triehlorodiphenylurea. Red. do 4-amino-2,5,4-trimethyldiphenylurea. Red. ..do 4-amino-5-methoxy-2-chlorodiphenylurea Red. dn 4-amino-2,5,3-trichlorodiphenylurea Red. do. 4-amino-2,5dimethyl-4-methoxydiphenylurea. Red. dn 4-amino-2,5-dimethyl-4-chlorodiphenylurea Red. do 4-31pgm-2,f-dimethyl-2-methoxy-4-chloro- Red.

1p eny urea.

4-aminodiphenylurea Red. 4-amino-5-chloro-2-methoxydiphenylurea Red. 4-amino-2,5-dimethyldiphenylurea. Red. 4-amino-2,4-dichlorodiphenylurea.-. Red. 4-amino-2,5-dichlorophenylmethylurea Red. 4-amino-2,5-dimetl1ylphenyl1nethylurea Red. 4-amino-2-chloro-5-methoxyphenylmethylurea Red.

4-a1ninophenylmethylurea Brown. 4-amino-2,5'dimethylphenylbenzylurea Red.

4-amino2-methoxy-2A,5-trichlorodiphenylurea... c rlet.

. 4-amino-2,4-dichlorodiphenylurea o. 4-amino-4-methoxydiphenylurea Red.

.. 4-amino-2',5-dichlorodiphenylurea Orange 4-amino-4-chlorodiphenylurea ed 56 2-111etfiery-4-chloro-5-methyl1iline 57 3-amino-4-chlorobenzoic acid-monomethylamide.

4-aminodiphenylurea 4-amino-2,5-dichlorodiphenylurea 4-amino-2-methoxy-5-chlorodiphenyl 4-amlno-2 4-amino-2,5-dimethyldiphenylurea R d 4-amino-2-methoxy-5,4-dichl0rodiphenylurea. 4-amino-4-chlorodiphenylurea 4-amino-2-chloro-5-methoxydiphenylurea Red. 4-amino-2,5-dimethyldiphenylurea Red. 4-amino-4-chlorodiphenylurea Red do 4-amino-2,fi-dimethyldiphenylurea 4-amino-2,5-dichlorodiphenylurea 4-aminophenyl-a-naphthylurea 4-amin0-2,5,4-trichlorodiphenylure Brownish re Red.

5 4-trichlorodiphenylurea Red.

Brownish red.

Red.

Bluish red;

Red.

I II III IV do 4-amino-2-methyl-4-chlorodiphenylurea Red. do 4-amino-2-methoxy-5,4-dichlorodiphenylurea Red. do 4-amino-4-ohlorodiphenylurea- Red. do .g.-. do 4-amino-2,fi-dimethyldiphenylurea Red. fin 4-amino-2-methyl-4-ohlorodiphenylurea-- Red. .d 4-amino-2,5,4-trichlorodiphenylurea Red. do 4-amino-2,5-dichlorodiphenylurea Red. do 4-amino-4-methyldiphenylurea Red. (in 4-ammo-2-chloro-5-methoxydiphenylurea Red. .do- 4-amino-2,5,4-trichlorodiphenylurea.. Red. do 4-am no-2,5-dimethy1-4-chlorodiphenylurea- Red. do 4-am no-4-chlorodiphenylurea Red. dn 4-am no2-methoxy-5,4-dichlorodiphenylurea Red. dn 4-am1no-2,5-dichlorodiphenylurea ed. do 4-aminodiphenylurea Red. o 4-amino-2,5,4'-trimethyldiphenylurea Orange.

EXAMPLE Z v 31.6 parts of 4 chloro 3 aminobenzoic acid-(2,5'-

dichloro) phenylamide are suspended in 150 parts of glacial acetic'acid; 30 parts of 30% hydrochloric acid are added and diazotization is carried out at to C. with 28.5 parts of 4 N sodium nitrite solution. After 30 minutes, the batch is'diluted with 300 parts of ice water, filtered, and the clear diazo solution is run into a solution of 18.8 parts of 2,3 hydroxyanphthoic acid in 300 parts of water and 14 parts of 30% sodium hydroxide solution at to 'C.; sodium carbonate solution is added at the same time, the pH value being kept at 8 to 8.5. After coupling, the batch is rendered acid to congo paper with hydrochloric acid, suction-filtered, washed free from'acid and dried. r

10.3 par-ts of the monoazo dyestuif monocarboxylic acid so prepared are heated for two hours at 110 to 115 C., while stirring with 400 parts of ortho-dichlorobenzene, 4 parts of thionyl chloride and 0.5 parts of di-' methylformamide. After cooling the reaction mixture, the uniformly crystalline monocarboxylic acid chloride of the dyestuff is isolated by filtration, washed with cold ortho-dichlorobenzene and benzene and then dried in vacuo at 50 to 60 C.

10.7 parts of this acid chloride are heated for 14 hours at 140 to 145 C. with 5.5 parts of N-(2,5-dimethyl-4- amino)-phenyl-N'-phenylurea-and 800 parts of orthodichlorobenzene. Subsequently,'the crystalline, sparingly soluble pigment is isolated by filtration while hot, washed with hot ortho-dichlorobenzene, alcohol and hot water,

and dried in vacuo at to C. The tained of the formula OH H30 1 is a red pigment which is sparingly soluble to insoluble'in thecommon solvents and which colours polyvinyl chloride films and lacquers red tints having an excellent fastness to light, migration and overstripe bleeding.

The monoazo dyestuff monocarboxylic acid chlorides, obtainable from the binuclear diazo components listed in column I of the following table and the coupling components listed in column II, can be reacted with 1 mol of the aromatic monamines containing urea groups listed in column III in the manner described in the first, second and third paragraphs of this example. Column IV indicates the tints obtainable with the pigments in polyvinyl chloride film.

product so ob- I II III IV 1 4-ehlgrg-3-aminobenzoic acid-(2,5'-dichloro)- 2,3-hydroxynaphthoic aoid 4-amin0-2,4-dichloro-5-methoxydiphenylurea Red.

am 1 e. 2 do dn 4-aminodiphenylurea Red. 3 do do 4-amino-2-ehloro-5-methoxydiphenylurea. Red. 4 4-amino-2,5-dimethyldiphenylurea Red. 5-- 4-amino2,4'-dichlorodiphenylurea Red. 6 -do do 4-amino 2,5,4-trimethyldiphenylurea Red. 7 do do 4-smino-4,2-dichloro-5-tri fluoromethyl- Orange diphenylurea. 8 do do 4amino-2,5-dichloro-4-methoxydiphenylurea. Red. 9 4-me tlhgl-3-aminobenzoic acid-(2,5-dichloro)- do 4-amino-2,5-dimethyldiphenylurea Red.

anli e. 10 do do 4-amino-2,S-dichlorodiphenylurea Red. 11-.. do do 4-amino-2,5,4-trimethyldiphenylurea. Red. 12' do 4-amino-2-chloro5-methoxydiphenylurea Red. 13 do i 4-emino-5,4-dich1oro-2-methoxydipheny1urea. Red. 14 4-metihox lnobenzoic aoid-(3-trifluorodo 4-aminodiphenylurea Bluish red,

me e. 1 d o do 4-amino-2,5-dimethyl-4'-chlorodiphenylurea Do. 16.- do do 4-amino-2,5-dimetl1yl-4-methoxydiphenylurea Do. 17 do 4-amino-2,S-dichlorodiphenylurea Do. 18 do do 4-amino-2,5,4-trichlorodiphenylurea D0. 19 do do 4-amino-2,5-dimethyldiphenylurea 1 Do. 20 do do 4-amino-2-methoxy-5-ehlorodiphenylurea Do. 21 4-ehloro-3-amiuobeuzoic acl do 4-amino-2,5-dichloro-4-methoxydiphenylurea- Red.

bomethoxy)-ani1ide. 22 do do 4-amino-4-ehlorodiphenylurea Red. 23 do do. 4-aminodiphenylurea Red. 24 do do 4-amino-2,5,4-trichlorodiphenylu.rea. Red. do 4-amino-2-methyldipheuylurea Red. do 4-amino-2,3-dicl1lorodiphenylurea Red. .do 4-amino-2-methoxy-5,4-diehlorodiphenylurea.- Red.

do 4-aminodiphenylurea Red. 4-arnino-2,5-dichlorodiphenylurea Red. 4-arnino-4-methoxydiphenylurea. Red. 4-amino-2,5-dimethyldiphenylurea. Red. inobenzoio acid-(5 rifluoro it-amino-2,5-dichlorodiphenylurea- Red. methyD-anilide. 33 do 4-aminodiphenylurea Red. 34 do do 4-amino-4-chlorodiphenylurea Red. 35 4-amino-2-methyl-4-chlorodiphenylurea Red. 36 3-nitro-4-aminobenzoic aeld-(2,5-dichloro)- .-...do 4-aminodiphenylurea Red.

anilide. t

, I II III p, IV v 37 4,6-dichloro-3-arninobenzoic aeid-(2,4-dido 4amino-2,fi-dimethyldiphenylurea- Red.

chloro)-anilide.

38 do do 4-amino-2-methoxy-5-chlorodiphenylurea 'Red.

39 do do 4-amino 2,4-dichlorodiphenylurea Red,

40 4-methy1-3-amlnobenzoic acid-(2'-ch1oro-5- 4-amino-2-methoxy-S-chlorodiphenylurea Bed.

4L- 4-amino-2,4'-dichlorodiphenylurea Red. 42-" 4-amin0-2,5-dimethoxydiphenylurea Red. 43 4-amino-4-carbomethoxydiphenylurea- Red. 44 do -amino-2,5-dimethylphenyl-methylurea Red.- 45 -methyl-S-arnlnobenzoic acid-(3-trifluorodo 4-amlno-4-methoxydiphenylurea Red.

methyl) -ani11de.

4-amino-2-methoxy-5-chloro diphenylurea 4-amino-2,5-dimethyldiphenylurea 4-amino-2,5-dichlorodlpheny1urea b o hydroxy-2-naph- 4-amino-2,5-4-trichlorodiphenylurea thoic acid.

50 do do 4-amino-2,B-dlmethyldiphenylurea Bluish red. 51 2-chloro-5-trifiuoromethylaniline 7-methoxy-3-hydroxy-2- 4-amino-2,E-dichlorodiphenylurea Do.

naphthoic acid. 52 do do 4-amlno-2,5-dimethyldiphenylurea- -earbomethoxy-3aminobenzoic acid. 2,3-hydroxynaphtho1c acid" 4-amino-4-chlorodiphenylurea 4-czglbethtiilxg-3-aminobenzoic acid-2,5-d ,do 4-amino-2,5-dimethyl-4-chlorodiphenylure c oran 1 e. 55 4-meth0xy-3-aminobenzoic acid-(3-trifiuoro- 7-bromo-3-hydroxy-2-naph- --do Blulshred.

methyl)-ani1ide. th acid. 56 do do 4-amino-2-methoxy-4,5-dich1orodiphenyluren Do. 57 do do 4-amino-2,4-dich1orodiphenylurea Do.

EXAMPLE 3 and 6 by regulating the supply of the solutions. The temperature must be between 35 and 40 C. This can be regulated by the addition of water to'the solutions of the components. The dyestuff suspension formed is filtered and the filter residue is washed. The residue is then stirred in a mixture comprising 110 parts of ethyleneglycol monoethylether and 100 parts of ortho-dichlorobenzene and the whole is filtered hot. The filter residue is washed successively with ethyleneglycol monoethylether and methanol and then dried in vacuo at 70 to 80 C. The product, which is obtained in almost quantitative yield, corresponds to the formula 16.2 arts of 2,5-dichloro-l-aminobenzene are diazotized in the usual manner with aqueous hydrochloric acid, ice and sodium nitrite.

40 parts of N'-[4-(2"-hydroXy-3"-naphthoylamino)- phenyl]-N-phenylurea are dissolved cold in a mixture of 200 parts of ethyleneglycol monoethylether and 20 parts of 30% sodium hydroxide solution. 1 part of the condensation product obtained 'from 8 mols of ethylene oxide and 1 mol of paratertiary-actylphenol is added to the solution and subsequently the naphthol is precipitated with 250 parts of 30% acetic acid while stirring well. Coupling is effected by addition of the diazo solution obtained as described in the preceding paragraph at a temperature of 30 to 35 C. while maintaining the pH at 5 to 6. Cou- N (313 pling is completed by stirring the batch at the same temperature for 2 hours, whereupon the pigment sus- N pension formed is rendered acidic to congo paper by the addition of hydrochloric acid and filtered. The filter H30 residue is washed with hot water until chlorine ions are no longer detectable in the filtrate. The residue is CONE 'O' dried in vacuo at 80 to 90 C. and the red pigment of the formula Cl It is a bluish red pigment which is sparingly soluble to insoluble in the common solvents and which colours N polyvinyl chloride film bluish red tints possessing an ii excellent fastness to light and migration.

EXAMPLE 5 OH 0 A mixture is prepared from 65 parts of stabilized pol- CONEGNHCONHQ vinyl chloride, 35 parts of dioctyl phthalate and 0.2 part of the pigment obtained in the manner described in the second paragraph of Example 1. The mixture so prepared is obtained in good yield. It is sparingly soluble to mis then Worked to and f f 7 minutes at Somme in the common solvents and colf'mrs POIYViPYl on a two-roller mill. A scarlet red film possessing a very chlo-idfe film as well as lacquers scarlet tints possessmg good fasmess m and migration is obtained goo astness to migration, overstnpe bleeding and What Is clalmed 18:

light.

EX P E 4 1. A monoazo pigmentX of the formula 23.3 parts of 4-methoxy-3-aminobenzoic acid-(3'-tri- 1 fluoromethyl)-anilide are dissolved warm in 45 parts of N glacial acetic acid and diazotized in the usual manner i& with aqueous hydrochloric acid, ice and sodium nitrite. X!

36.5 parts of N-[2',5'-dimethyl-4'-(2"-hydroxy-3"- OH naphthoylamine)-phenyl] N (4-chlorophenyl) urea Y1 are dissolved cold in a mixture of 80 parts of ethylene- CONH glycol monoethylether and 66 parts of 30% sodium hydroxide solution. The two solutions, if desired, after dilution with water, are conducted continuously to a mixing nozzle where coupling takes place instantaneously. in which R is a member selected from the group con The pH value in the mixing nozzle is kept at between 5 sisting of lower alkyl, benzyl, phenyl and naphthyl and Y2 NHCONHR phenyl and naphthyl substituted by chlorine or bromine, lower alkyl, lower alkoxy, lower carbalkoxy, trifluoromethyl or lower alkanoylamino groups, X is a member selected from the group consisting of hydrogen, chlorine and bromine atoms and lower alkoxy groups, X is a member selected from the group consisting of hydrogen, chlorine and bromine atoms, X and X each represent hydrogen, chlorine and bromine atoms, lower alkyl, lower alkoxy, phenoxy, nitro, cyano, lower carballroxy, carbophenylamido, lower alkanoylamino or trifluoromethyl groups, Y and Y each represent members selected from the group consisting of hydrogen, chlorine and bromine atoms, lower alkyl, trifluoromethyl, and lower alkoxy groups.

2. A monoazo pigment as claimed in claim 1 of the formula in which V is a member selected from the group consisting of a chlorine atom, a lower alkyl, lower al'koxy, and lower carbalkoxy group, W is a member selected from the group consisting of hydrogen and chlorine atoms and Z is a member selected from the group consisting of chlorine atoms, lower carbalkoxy groups and the group of the formula in which 2,, is a member selected from the group consisting of hydrogen, chlorine and bromine atoms,Z and Z represent members selected from the group consisting of hydrogen, chlorine and bromine atoms, lower alkyl, lower alkoxy, lower carbalkoxy, nitro, cyano and trifluoromethyl groups, 2, is a member selected from the group consisting of hydrogen, chlorine and bromine atoms, 2,, and 2;, represent members selected from the group consisting of hydrogen, chlorine and bromine atoms, lower alkyl, lower alkoxy, lower carbalkoxy, nitro, cyano, trifluorornethyl and lower alkanoylamino groups.

3. The dystulf as claimed in claim 1 of the formula 14 4. The dyestuff as claimed in claim 1 of the formula 0 it l c oNH-O-Nrro ONH- 5. The dyestutr as claimed in claim 1 of the formula N or lg I ONH err 01 CONH 0H Cl CONH 7. The dyestuff as claimed in claim 1 of the formula OH on, o ONHONHCONH-CH:

References Cited UNITED STATES PATENTS 2,199,048 4/1940 Graenacher et a1. 260-203 FOREIGN PATENTS 924,518 4/ 1963 Great Britain,

17,213 7/1956 Germany;

FLOYD D. HIGEL, Primary Examiner US. Cl. X.R.

CASE 5670/E ggigg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 72, 3 Dated October lib 1969 Inventor(s) Karl Roneo et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 14, claim 5, bottom right-hand portion of formula should read:

CFB

SEGNEB MW QEALH' mi: 2 1% (SEAL Atteat:

dna-6M, Fletcher In WILLIAM E. saaumm, .m-

I ucefin Offi Gemiaaioner of Patents J 

